Process for manufacturing iso-



3,037,979 PROCESS FOR MANUFACG ISO- CY DERIVATIVES Kenichi Fukui, 21 Tanaka-oicho, Sakyo-ku, Kyoto City, Japan, and Hisao Kitano, 36 Minaml-mikunlgaokacho l-cho, Sakai City, Japan No Drawing. Filed Apr. 23, 1958, Ser. No. 730,252

Claims priority, application Japan Sept. 9, 1957 5 Claims. (Cl. 260-248) Derivatives of I and II in which the three hydrogen atoms have been replaced by various organic radicals will be hereinafter called cyanuric acid derivatives Their molecular structures are respectively of the type III or IV below, each of which represents a difierent stable compound from the other.

Besides, the additional two types represented by III and IV', the presence of which may be theoretically assumed, have been actually found by the inventors together with the derivatives of III and IV as the products of the reaction under certain conditions. In such cases, the derivatives of III and IV may be included in so-called cyanuric acid derivatives."

O R O t t i P RO-C N/COR O-C\N/CO (III) (IV) 0 R O a. i N N RN N-R Roi on. a...

(III) (I V) Each compound of these types, the isomer of the others, can be isomerized by some suitable operations. The type III compounds for example may be converted to the type IV by heating. In general, compounds of the type III are referred to as cyanurates or cyanuric esters, while compounds of the type IV as isccyanurates or isocyanuric esters.

3,937,979 Patented June 5, 1952 The heretofore known procedures for manufacturing cyanuric esters mostly consist in subjecting acid halides such as cyanogen chloride, cyanogen bromide, cyanuric chloride or bromide or the like to a reaction with sodium alcoholate or with an alcohol in the presence of sodium hydroxide. It has been also reported that trimethyl cyanurate is obtained by the reaction of silver cyanurate with methyl iodide. Isocyanurates i.e. esters of isocyanuric acid have been manufactured by isomen'zing esters of cyauuric acid or by polymerizing esters of isocyanic acid. It has been also reported that they are formed by the reaction of metal cyanates or cyanurates with potassium alkyl sulfate or esters of inorganic acids, accompanying the corresponding esters of cyanuric acid. Some of these methods, however, cannot dispense with poisonous materials, while the others may be carried out only with poor yield or otherwise require a complicated and inconvenient technique. All these are accordingly not industrial methods of high merit.

Since cyanuric derivatives include some compounds which have drawn attention of late as valuable industrial materials especially as starting substances or intermediates in the organic or macromolecular chemical industry, discovery of any safe and inexpensive procedure for manu facturing said derivatives has been pressingly sought after.

The inventors have found that cyanuric acid derivatives of superior quality may be simply produced with better yield and at a lower cost, in a close connection with petrochemical industry, if organic halogen compounds having at least a halomethylene or halomethyl group and neither carboxyl nor sulfonic acid group are brought to the reaction with alkali cyanates in the presence of such organic compounds as have a nitrogen or sulphur atom combining with one or two alkyl groups and with no hydrogen atom.

The said organic halogen compounds having at leasta halomethylene or halomethyl group and neither carboxyl nor sulfonic acid group may be represented by the general Formula V wherein A and B stand for respectively a hydrogen atom, an aliphatic or aromatic hydrocarbon radical, a hydrocarbon radical containing both aliphatic and aromatic group, or any derivative of such hydrocarbon radical as contains neither carboxyl nor sulfonic acid group, said groups 'A and B being allowed to connect directly with each other in a cyclic form, while X indicates a chlorine, bromine or iodine atom. In case where A or Bis a derivative of a hydrocarbon radical, it may contain additional halogen atoms and such compound V may accordingly have two or more halogen atoms. Some examples of such compounds are the dihaloalkanes, dihaloketones, polyhaloalkanes, dihaloolefins, dihaloethers and the like. It will he certainly understood that an organic halogen compound of the type V is not necessarily used alone in a process in accordance with this invention, and a mixture of compounds of said type, for instance a chlor'oparaflin mixture to be produced by chlorination of kerosene, may be used. Exclusion of cases, where the group A or B contain any carboxyl or sulfonic acid group, is due to the fact that no cyanuric acid derivative can be obtained in;

aromatic radical or a derivative thereof.

such cases. In cases where A or B is a derivative of a hydrocarbon radical, however, it may contain one or more heteroatoms which are not constituent atoms of any acid group, for instance oxygen atom of ether form or sulphur atom of thioether form, or even other heteroatoms such as silicon atom. V

The aforesaid alkali cyanates signify lithium cyanate, sodium cyanate, potassium cyanate, ammonium cyanate or their mixtures, which are not necessarily pure. Alkali cyanates which contain a moderate amount of impurities may be used, while those containing a considerable amount of impurities sometimes need partial purification in advance. Some foreign matters such as inorganic iodides I which accelerate'.the rate of reaction may be preferably contained in or added to said alkali cyanates.

The aforesaid organic compounds which have a nitrogen or sulphur atom combining with one or two alkyl groups'and with no hydrogen atom may be represented by the following general formulae:

wherein R and K: respectively indicate an alkyl group,

R' a hydrogen atom, an aliphatic or aromatic hydrocarbon radical or a derivative thereof and R an aliphatic or R1, R2 and R" may be either identical to or diiferent from each other in one molecular formula. Two or more Rs may be attached to one and the same benzene molecule. In the above-listed formulae, two alkyl groups may unite with each other so as to form a heterocycle. The abovedescribed organic compounds may be used either as a sole solvent or as mixed solvents in the reaction in accordance with this invention. Several typical examples of said organic compounds which have nitrogen or sulphur atom combining with one or two alkyl groups and with no halogen atomare dimethyl-formamide', diethylromamide, N,-N-dimethyl-acetamide, N,N-dimethyl-benzenesulfonamide, dimethyl-sulfoxide, dimethyl-sulfone, acetyl-pipelidine, acetyl-morpholine, N-methyl-diacet-amide, N- methyl N phenyl-benzene-sulfonamide, tetra methylene-sulione and the like." of such compounds may be industrially produced at'lower costs and commercially supplied at moderate prices. High-priced solvents may and should beutilized together with cheaply available solvents in a mixed state;

In this invention, use of such organic compounds as the solvents as have a nitrogen or sulphur atom combined with hydrogen is excluded, since it may usually produce such undesired products as N-alkyl-ureas, thiocarbamates,-N-acyl-N-alkyl ureas, formation oi the desired cyanuric acid derivatives being thereby prevented. However, admixture of a small amount of said comin' the solvents as impurities may be allowed in carrying out this invention, under the conditions of industrial'advantag'eousness in spite of decreasing yield in some. degrees. Mingling of other impurities in the solvent may also be considered in a similar way.

The fundamental reaction in processes in accordance with the present invention are represented in principle by the following formulae:

in which RX represents organic halogen compounds and MCNO alkali cyanates. Reactions of the type 1 and 2 do not always proceedsuccessfully except in the presence of special solvents. The inventors have found that the afore-mentioned organic compounds which have nitrogen or sulphur atom combined with one or two alkyl groups and with no hydrogen atom have such a solvent action that can smoothly promote the reactions 1 and 2. Processes according to this invention should be discriminated from the well-known methods in using these specific solvents. Use of these solvents facilitates the operation to a considerable extent, since it enables the reaction to be carried out smoothly even at the atmospheric pressure. Such efiect can be attained neither without solvents nor with other known solvents. This is the point in which the methods according to this invention are recognized as extremely convenient and favorable from the industrial standpoint of view.

' Said organic solvents may be synthesized in a large scale from either petroleum or coal. They may be easily purified and made less corrosive. The cyanuric acid derivatives to be produced according to this invention may be separated from the reaction mixture by such simple treatments as distillation, filu'ation, decantation, sedimentation, extraction or the like; The said organic solvents also can be easily recovered by these operations.

Inmost cases, the reactions of this invention may be carried out at temperatures lying within the range of 30- 200 C. under atmospheric pressure by applying the solvents having suitable melting and boiling points. In .order to accelerate the reaction rate or to treat a starting substance of lower reactivity, the reaction temperature may be raised up to ZOO-300 C. If it is desired to apply .a low-boiling organic halogen compound as the solvent, it is also possible to use an autoclave as the reaction vessel.

Catalysts such as trialkylamine or trialkylphosphine are often required for the polymerization of aliphatic isocyanates or the reaction of organic halogen compounds with metal cyanates in the known processes. In accordance with this invention, however, such catalysts are quite unnecessary.

In order to introduce a desired group R into the cyanuric acid derivative to be produced, an organic compound containing the isocyanate group R NCO may be added to the reaction mixture according to this invention.

Both the reactions indicated by the Formulae 1 and 2 generally proceed simultaneously, resulting in the formation of a mixture of cyanuric ester III and isocyanuric ester IV, and under, certain conditions, other esters of cyanuric acid Ill and IV. The ratio of those two or four forms of esters to be formed generally depends mainly upon the molecular structure of startingv material. The ratio, however, may be controlled to some extent by adoption of the proper temperature of reaction, the proper duration of reaction and/ or selection of the proper solvent. Application of an especially high-boiling solvent, an

elevated temperature of reaction under pressure or prolonged heating can increase the isocyanura-te content in the reaction product. It is also possible to convert the cyanuric ester once formed into isocyanuric ester partially or almost completely.

The cyanuric esters of the form III to be produced in accordance with this invention may be transformed into various valuable materials by bringing them into reaction, under appropriate conditions, with ammonia, amines, alcohols, 'glycols or the like. The isocyanuric esters form such interesting compounds as substituted ureas or substituted biurets, when they are subjected to hydrolysis or aminolysis under suitable conditions.

If unsaturated organic halogen compounds are adopted as the starting materials in a specific embodiment of this invention, cyanuric acid derivatives containing unsaturated hydrocarbon radicals may be obtained. For instance, a mixture of triallyl cyanurate, triallyl isocyanurate, and other triallyl esters of types III and IV is formed from allyl bromide. These unsaturated esters, either in the mixed state or in separated state, give a beautiful, heat-resistant resin, when they are subjected to polymerization the procedures of which per se are well known in the art. The radical polymerization process, the ionic polymerization process, the polymerization process by cationic catalysts and metals, and irradiation of radiative or particle rays may be applied to the polymerization of said unsaturated cyanuric esters. Copolymer resins, which have various excellent characteristics, also may be obtained, if the abovesaid unsaturated esters are subjected to polymerization with monomers of other compounds. Moreover, said unsaturated esters can be utilized to give bridge structures to other unsaturated polyester resins.

In another specific embodiment of this invention, saturated aliphatic halogen compounds having three or more carbon atoms in its molecule may be also used as the starting material, producing a mixture of esters of cyanuric acid which contain, per molecule, three alkyl radicals having three or more carbon atoms respectively. Thus produced esters, either in the mixed state or in an isolated state, serve as favorable plasticizers for various high molecular substances such as phenolic resins, vinyl resins, polystyrene resins, polyester resins, furfural resins,

acryl resins, urea resins, melamine resins, polyamide resins, cellulose derivatives, protein or protein-like substances.

In a finthermore specific embodiment of this invention, fluorine-containing organic halogen compounds may be used as the starting material. In such a case, fluorinecontaining cyanuric and isocyanuric esters are obtained which can be utilied as raw materials or intermediates for industrial chemicals.

Another furthermore interesting embodiment of this invention is use of such organic compounds as have two or more halomethylene or halomethyl groups in a molecule as the starting substance. The molecular weight increases in succession as the following reactions 3 and 4 or 5 and 6 proceed, resulting in formation of high molecular cyanuric acid derivatives. The formula XD-X represents said organic compound having two halomethylene or halomethyl groups.

l D-O 3MCNO l) l) ll (6) It will be easily understood that both the cyanuric and isocyanuric ring structures may co-exist in one macromolecule and also that the O-ester structure may exist together with the N-ester in the same triazine ring, respectively corresponding to the structures III and IV. As the polymerization gradually proceeds, viscosity of the reaction mixture remarkably increases and finally gelation sets in.

The thus formed polymer per se has, end groups such as halogen atoms, isocyanate radicals and sometimes cyano or iso cyano groups according to the kind of solvents used. Since such end groups include some unstable ones which give unagreeable properties to said polymer, the following chemical treatments are often recommended. Said polymer may be stabilized or reformed and improved, immediately after its formation, by treating it with the substances having active hydrogen, such as water, alcohol, glycols, phenols, aldehyde, organic acids, metal hydroxides, organosilanols, compounds having crystallization water, ammonia, amines, inorganic bases, mereaptans, inorganic acids, high molecular substances having active hydrogens, at temperatures lying within 0-300C. under atmospheric or higher pressure. Such treatments may be efiectively carried out in two or more steps; for instance, 75 first with water and then with acetic anhydride.

Molecular weights and physical properties of the polymer just formed depend upon the reactants, the solvents, the reaction temperature and the reaction time, the latter, however, being the most important factor. As the reaction time is prolonged, appearance of the polymer produced varies ranging from a syrup-like state to a hard gel, passing through a millet-jelly-like state, grease-like state, soft gel and jelly-like gel. The polymers in each step above-mentioned may be utilized for various purposes according to respective characteristic properties. The polymers of relatively low molecular weight may be used as or for lubricants, plasticizers, pastes, paints or the like,

while those of medium molecular weight as or for fillers,

packing substances, sponges, films, substitutes for synthetic rubbers, heat-resistance improver of synthetic resins or the like. The polymers of high molecular weight per se, or with suitable plasticizers mixed, or together with other high molecular substances or with inorganic substances, may be moulded at temperatures ranging from 150 C. to 450 C. under a pressure of more than several atmospheres, thus forming various kinds of artificial resin having characteristics respectively. When moulded with glass fibers mixed, a hard, beautiful and extremely heatresistant resin product is obtained.

If suitable amounts of active hydrogen-containing substances, inactive solvents, sulphur compounds or monomers of other compounds are mixed in advance in the reaction mixture of the afore-mentioned procedure, resinous substances having specific uses may be produced.

It will be understood without furthermore superfluous explanation that cyanuric acid derivatives having three halomethylene or halomethyl groups maybe used as the afore-mentioned organic compounds having two or more halomethylene or halomethyl groups and that the aforementioned macromolecular substances having the good quality can not be produced efficiently and easily without using the solvents hereinbefore specified.

The following examples illustrate the invention but are not to be construed as limiting the same:

Example 1 In a flask equipped with a stirrer, a dropping funnel, a reflux condenser and a thermometer were placed 300 g. of dimethylformamide and 100 g. of potassium cyanate.

The mixture was heated to 135-137 C. and stirred, while oftheoretical amount). 7 H

Example V V Isobutyl bromide was used instead of ethyl bromide in the foregoing example. Tri-isobutyl-isocyanurate, B.PL 172-178 C./ mm. Hg, was obtained with 82' percent yield. I H Example 3 1 mole of allyl bromide was used in place of ethyl bromide in Example 1. A mixture of triallyl esters of cyanuric acidwas obtained with 90 percent yield.

Example 4 In a round-bottomed and four-necked flask of 1 liter capacity, fitted witha mercury-sealed mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel were placed 300 g. of dimethyl-formamide and 80 g. of powdered sodium cyanate. The mixture was maintained at l45-l50 C. and stirred during addition of 1 20 g. of

allyl bromide from the dropping funnel, requiring about forty minutes. The reaction was complete after stirring at the same temperature for additional two hours. After cooling, the reaction mixture was filtered by suction an'd the residue was washed with two cc. portions of the reaction solvent. The combined filtrate was distilled through a fractionating column. A mixture, boiling at -165 C./ 6 Hg, of triallyl esters of cyanuric acid was obtained with 92 percent yield.

Example 5 300 g. of diethyl-formamide was used in lieu of di methyl-formamide in Example 4. A mixture of triallyl esters of cyanuric acid was obtained with 95 percent yield.

Example 6 Instead of dimethyl-formamide in Example 4, 300 g. of N-methyl-diacetamide was used. A mixture of triallyl esters of cyanuric acid was obtained with 85 percent yield.

Example 8 a 300 g. of formyl-piperidine was used as a solvent in place of dimethyl-formamide in Example 4. A mixture of triallyl esters of cyanuric acid was obtained with 83 percent yield.

Example 9 v 300 g. of acetyl-m'orpholine was used in lieu of dimethyl-formaniide in' Example 4., A mixture of triallyl esters of cyanuric acid was obtained with 92 percent yield.

Example 10 A mixture of 150g. of dimethyl-sulfoxide and 150 g. dimethyl-sulfone, instead of dimethyl-forma'mide, and 76 g. of allyl chloride, instead of allyl bromide, respectively in Example 4, were used. A mixture of triallyl esters of cyanuric acid was obtained with 78 percent yield.

Example 11 A mixture of 150 g. of tetramethylene-snlfoxide and 150 g. of tetramethylene-sulfone was used as the solvent instead of dimethyl-formamide in Example 4. A mixture of triallyl esters of cyanuric acid was obtained with 80 percent yield. Example 12 In a thick-walled Pyrex tube were placed 30 g. of dimethyl-acetarnide, 9 g. of potassium cyanate and 5 g. of methyl chloride and then said tube was sealed. It was heated at 150 C. for 3 hours on a shaker. After cooling, the reaction mixture was diluted with ether and then filtered. The filtrate was distilled under diminished pressure to remove the solvent. The product was isolated by recrystallization from water. The yield of trimethyl-isocyanurate was 68 percent of the theoretical amount.

Example 13 30 g. of dimethyl-benzene-sulf-onamide was used instead of dimethyl-acetamide in Example 12. Trimethylisocyanurate was obtained with 45 percent yield.

Example 14 .7 g. oflithium cyanate was used instead of potassium cyanate in Example 12. Trimethyl-isocyanurate was obtained with 53 percent yield.

Example 15 8 g. of sodium cyanate was used instead of potassium cyanate in Example 12. Trimethyl-isocyanurate was obtained with 61 percent yield.

Example 16 A mixture of 8 g. of sodium cyanate and 1 g. of

9 sodium iodide was used in lieu of potassium cyanate in Example 12. Trimethyl-isocyanurate was obtained with 78 percent yield.

Example 17 In a reactor, fitted with a mechanical stirrer, a reflux condenser and a thermometer were placed 50 g. of dimethyl-formamide, 50 g. of dimethyl-acetamide, 6 g. of butyl iodide, 11 g. of allyl iodide and g. of potassium cyanate. The mixture was kept at 8590 C. while stirring. After 3 hours, the reaction was complete. Mixed allyl-butyl esters of cyanuric acid was obtained with 67 percent yield as the main product.

Example 18 In a reactor, fitted with a mechanical stirrer, a dropping funnel, a thermometer were placed 300 g. of acety1- piperidine, 20 g. of lithium cyanate, 80 g. of potassium cyanate. The mixture was heated to 150-155 C. and stirred, while 126.5 g. of benzyl-chloride was added dropwise over a period of one hour. The mixture was maintained at the same temperature for additional 2 hours before cooling. The reaction mixture was filtered and the filtrate was distilled under reduced pressure. The obtained were tribenzyl esters of cyanuric acid.

Example 20 In a reaction vessel, fitted with a stirrer, a thermometer and a reflux condenser wereplaced 400 cc. of dimethylformamide, 200 g. of potassium cyanate, and 127 g. of 1,4-dichlorobutane. The mixture was maintained at 100 C. and stirred for 8 hours before cooling. The reaction mixture was filtered with suction and the filtrate was distilled under reduced pressure. After removal of the solvent, the residue, soft jelly material, was replaced into mixing rolls and well blended in air. The blended material was injected into a metal mould and kept at room temperature for several days. The material remarkably expanded to a spongy cake, which was washed and dried. The spongy product, which has mainly poly(butylenediisocyanurate) structure, has very stable, high heat-resistant and sound-arresting properties and is suitable for building materials. If the foamy pores of the spongy material are filled with styrene containing 2 percent of peroxide catalyst and then cured at 60 C. for several days, extremely hard plastics may be obtained.

Example 21 Example 22 In the process described in Example 20, the reaction mixture was maintained at 140 C. while stirring for 3 hours. After cooling, the obtained gel was thrown into water and crushed therein. The crushed material was boiled in water for 10 hours and the precipitatewas filtered with suction, washed with water, dried and powdered. The white powder gives clear brown plastics when moulded at 350 C. A reinforced laminate may be obtained if moulded together with glass fibers. Valuable plastics to be used for various purposes such as building, industrial, domestic and the like materials may be obtained when said white powder is mixed with various kinds of fillers or pigments and moulded at an elevated temperature.

Example 23 In a reaction vessel fitted with a thermometer, a reflux condenser and a mechanical stirrer were placed 94 g. of 1,2-dibromoethane, g. of potassium cyanate and 250 g. of dimethyl-sulfoxide. The mixture was maintained at -140 C. and stirred for 3 hours and thus formed gel was put into water and crushed. The precipitate was filtered, thoroughly washed with boiling water, dried at 100 C. under diminshed pressure and pulverized. Thus obtained powder consists of high molecular weight mixture and can be moulded at 380 C.

Example 24 Instead of 1,2-dibromoethane in Example 23 was used 79 g. of trimethylene-chlorobromide. Thus obtained was resin powder which can. be moulded at 360 C.

Example 25 I Instead of l,2-dibromoethane in Example 23 was used 56 g. of propylene-dichloride. The obtained product can be moulded at 380 C.

Example 26 72 g. of bis-(B-chloroethyD-ether was'used instead of 1,2-dibromoethane in Example 23, the corresponding cyanurate resin was obtained. It. was found to. be moulded at 270 C.

Example 27 When 100 of bis-(4-chlorobutyl)-ether was used instead of 1,2-bromoethane in Example 23, a resin which may be moulded at 300 C. was obtained.

Example 28 When 95 g. of bis-(fi-chloroethyl)-sulfone was used in place of 1,2-dibromoethane in Example 23, a resin which may be moulded at 320 C. was obtained.

Example 29 reduced pressure to about cc. The condensate was added with 30 cc. of diethyl-amine and refluxed for 1 hour. The resulting mixture was poured into water and the precipitate was washed with water anddried. After pulverizing, a polymerof cyanuric acid derivatives of kerosene was obtained as a white powder capable of being moulded at 300 C. When mixed with polystyrene, polyvinylacetate or polyacrylonitrile powder, they can be moulded at 200-300 C. giving new plastics useful for various purposes.

l Example 30 70 g. of chlorinated pentane was used in place of chlorinated kerosene in Example 29. The obtained polymer of cyanuric acid derivatives was found to be moulded at 280-310 C. i

- Example 3] The reaction was carried out in an autoclave without 1 1 sodium iodide in Exam'ple29. The reaction mixture was kept at 150-155 C. while shaking for 2 hours. The obtained product, a polymer of cyanuric derivatives, was found to'be moulded at 370-410 C.

, Example 32 Example 33 p a 1 A mixture of alkyl-chlorides, containing hexyl-, octyl-, decyland dodecyl-chlorides was prepared from palm-oil alcohol and thionyl-chloride In a reaction vessel fitted with a mechanical stirrer, a

12 35. The'product was found to be moulded at 370-400" I C. to form a heat-resistantresin.

dropping funnel and a reflux condenser were placed 500 .g. of dimethyl-formarnide and 200 g'. of sodium cyanate. The mixture was maintained at 145-147 C. and stirred while adding dropwise 1 00 g. of said mixture of alkyl chlorides requiring one hour. The mixture was kept'at the "same temperature for additional onehour before cooling. The reaction mixture was filtered and the filtrate was distilled under reduced pressure. -After re- 7 moval of dimethyl-formamide, waxy material of cyanuric acid derivatives was obtained, the yield being 80' g. The waxy material may be used as a plasticizer or aheating medium. a

Example 34 Q In a reaction vessel fitted \m'th a revolving hopper, a

reflux condenser, a mechanical stirrer and a thermometer,

were placed 254 g. of 1,4-dich1orobutane, 400 g. of dimethyl-formamide and 100 g. of acetyl-morpholine. The

mixture was kept at 130-140 C. and stirred,while adding 150 g. of potassiumcyanate through the hopper requiring 2 hours. The reaction mixture was kept at the same temperature for additional half an hour before cooling. The resulting reaction mixture was filtered and the filtrate was distilled underreduced pressure.

oxide; The solution was maintained at 135140 C. and stirred, while adding 100 g. of potassium cyanate action mixture was treated as described in Example 21. The product may bemoulded at 370 C. to form a clear brown plastic material.

7 Example 36 When 282 g. of 1,5-dichloropentane was used instead of 1,4-dichlorobutane in Example 34, tris-(S-chloropentyl)-isocyanurate, B.P. 219224 C./5 mm. Hg, was obtained with 67 percent yield.

0 Example 37 A mixture of 100 g. of tris-(4- chlorobutyl)-isocyanurate and 100 g. of tris-(S-chloropentyl) -isocyanurate was dissolvedin 700g. of d-imethyl-formamide. The solution at 340-35 0 C to form a clear brown plastic material.

. Example 38 130 g. of tris-(B-chloroethyl)cyanurate and 150 g. of

sodium cyanate were brought into. reaction as in Example What is claimed is:

1. A method of producing triallyl isocyanurate; comprising the step of reacting sodium cyanate with allyl bromide in the presence of about 1 to 15 moles, per mole of sodium cyanate initially present in the reaction mixture, of N-acetyl morpholine for a period between about 1 and 5 hours at a temperature. between 100 C. and 160 C.

2. A method of producing triallylisocyanurate; comprising the step of reacting sodiurn'cyanate with allyl bromide in the presence of about 1 to 15 moles, per mole of sodium cyanate initially present in the reaction mixture, of dimethylsulfoxide for a period between about 1 and 5 hours at a temperature between 100 C. and 160 C.

3. The method of producing triallyl isocyanurate; comprising the step of reacting sodium cyanate with allyl bromide inthe presence of aboutfl to 15 moles, per mole of sodium cyanate initially present in the reaction mixture, of tetramethylenesul-foxide for a period between 1 isocyanurate ring; comprising the step of. reacting an alkali metal cyanate with an organic halogen compound selected from the group consistingof alkyl, alkenyl and ara lkyl halide having a maximum of 12 carbon atoms and at least one hydrogen atom. on the halogen substituted carbon atom, said halogen atomhaving an atomic weight of atleast 35, in the presence of about 1 to 15'moles per mole of the alkali metal cyanate initially present in the reaction mixture, of a compound selected from the group consisting of N-formylmo'r'pholine, N-acetylmorpholine,

. dimethylsulfoxi-de, dimethylsulfone, tetrarnethylenesulfthrough the hopper requiring about one hour. The rep pholine, N-acetylmorpholine,

oxide and tetramethylenesulfone, for a period of more than 1 hour at a temperature between C. and C.

5. A method of producing a polymer having more than one isocyanurate ring; comprisingthe step of reacting an alkali metal cyanat e with an organic halogen compound having a maximum of 12 carbon atoms and being selected from thegroup consisting of alkylene dihalide, aralkylene dihalide, vbis (haloalkyl) ether, bis (halo- ,alkyl) sulfone, tris (haloalkyl) cyanurate and tris (haloalkyl). isocyanurate having-at least 'one hydrogen atom on each halogen substituted carbon atom, each halogen atom having an atomic Weight of at least 35, in the presence of 1 to 15 moles,'per mole of alkali metal cyanate initially present in the reaction mixture, of a compound References Cited in the file of this patent UNITED STATES PATENTS 2,536,849, Kaiser Jan. 2, 1951 2,697,720 Kaiser Dec. 21, 1954 2,801,244 Balon Q July 30, 1957 2,866,801 1 Himel et a1. Dec. 30, 1958 2,866,803 De Pree Dec. 30, 1958 2,870,163 Davis et a1. Jan. 20, 1959 2,870,216 Sorensen et a1 Jan. 20, 1959 2,900,381 Thatcher Aug. 18, 1959 2,901,497 Delfs et a1. Aug. 25, 1959 2,934,525 Fekete Apr. 26, 1960 OTHER REFERENCES Bergmann: The Chemistry of Acetylene and Related Compounds, page 80, Interscience Publishers Inc., NY. (1948). 

4. A METHOD OF PRODUCING A COMPOUND HAVING ONE ISOCYANURATE RING; COMPRISING THE STEP OF REACTING AN ALKALI METAL CYANATE WITH AN ORGANIC HALOGEN COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL AND ARALKYL HALIDE HAVING A MAXIMUM OF 12 CARBON ATOMS AND AT LEAST ONE HYDROGEN ATOM ON THE HALOGEN SUBSTITUTED CARBON ATOM, SAID HALOGEN ATOM HAVING AN ATOMIC WEIGHT OF AT LEAST 35, IN THE PRESENCE OF ABOUT 1 TO 15 MOLES PER MOLE OF THE ALKALI METAL CYANATE INITIALLY PRESENT IN THE REACTION MIXTURE, OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF N-FORMYLMORPHOLINE, N-ACETYLMORPHOLINE, DIMETHYLSULFOXIDE, DIMETHYLSULFONE, TETRAMETHYLENESULFOXIDE AND TETRAMETHYLENESULFONE, FOR A PERIOD OF MORE THAN 1 HOUR AT A TEMPERATURE BETWEEN 100*C. AND 180*C.
 5. A METHOD OF PRODUCING A POLYMER HAVING MORE THAN ONE ISOCYANURATE RING; COMPRISING THE STEP OF REACTING AN ALKALI METAL CYANATE WITH AN ORGANIC HALOGEN COMPOUND HAVING A MAXMIUM OF 12 CARBON ATOMS AND BEING SELECTED FROM THE GROUP CONSISTING OF ALKYLENE DIHALIDE, ARALKYLENE DIHALIDE, BIS (HALOALKYL) ETHER, BIS (HALOALKYL) SULFONE, TRIS (HALOALKYL) CYANURATE AND TRIS (HALOALKYL) ISOCYANUARATE HAVING AT LEAST ONE HYDROGEN ATOM ON EACH HALOGEN SUBSTITUTED CARBON ATOM, EACH HALOGEN ATOM HAVING AN ATOMIC WEIGHT OF AT LEAST 35, IN THE PRESENCE OF 1 TO 15 MOLES, PER MOLE OF ALKALI METAL CYANATE INITIALLY PRESENT IN THE REACTION MIXTURE, OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF N-FORMYLOMORPHOLINE, N-ACETYLMORPHOLINE, DIMETHYLSULFOXIDE, DIMETHYLSULFONE, TETRAMETHYLENESULFOXIDE AND TETRAMETHYLENESULFONE, FOR A PERIOD OF MORE THAN 1 HOUR AT A TEMPERATURE BETWEEN 100* C. AND 180* C. 